JP6906001B2 - Gravure or flexo ink, and its use - Google Patents

Description

The present invention relates to gravure or flexographic inks preferably used for packaging materials, especially laminated laminates.

Gravure or flexo ink is widely used for pattern printing for the purpose of imparting beauty and functionality to the printed material, but in recent years, it has become more diverse in packaging, advanced packaging technology, and used as an organic solvent. Demands for printing inks are diversifying year by year, such as efforts to address environmental issues from the legal and regulatory aspects represented.

Furthermore, as a measure against global warming, the reduction targets of each country were submitted at the 21st Conference of the Parties to the United Nations Framework Convention on Climate Change (COP21) held in 2015, and Japan will have a greenhouse by 2030 compared to 2013. A draft promise to reduce greenhouse gases by 26% was submitted (Patent Document 1). To achieve this, for example, there is the concept of carbon neutral. When this is done, if biomass raw materials such as plant raw materials are used and the amount of carbon dioxide emitted by combustion and the amount of carbon dioxide absorbed and fixed by the growth of plants are the same, carbon dioxide in the air Does not increase. Therefore, as the raw material of gravure or flexo ink that can be used for packaging materials for films, plant-derived (biomass-derived) materials are used, that is, the biomass degree of gravure or flexo ink is not increased to the extent that carbon dioxide in the air is not increased. There is an urgent need for efforts to improve the above.

On the other hand, among gravure or flexographic inks, those used especially for laminated laminates often use polyurethane resin in order to maintain and improve the laminated strength. This is because the polyurethane resin can be widely and freely designed from a hard and tough coating film to a flexible and elastic coating film by appropriately selecting isocyanates, polyols and the like as raw materials thereof. However, even when a biomass-derived polyurethane resin is used, at least the same performance as the conventional one can be maintained, and further improvement in characteristics is required in the future. Therefore, among polyurethane resins, various studies have been conducted on biomass-derived polyester polyol structures, which are raw materials for the constituent units of polyurethane resins, in order to improve printability and laminate strength (Patent Documents 2 and 3).

For example, controlling hygienic conditions such as taste and odor in the contents of a packaging bag using a laminated laminate is one of the important performances. When conventional petroleum-derived inks of poor quality are used, problems such as by-products of ink raw materials, decomposition products, trace impurities, etc. are transferred to the contents, elution into the contents, deterioration of quality such as odor, etc. In some cases.
For example, in Patent Document 4, the main component eluted in the content is cyclic dicarboxylic acid, but other compounds may have a large effect on the odor and taste of the content even if the amount of elution is small. ..

JP-A-2018-062642 WO2018 / 110664 Pamphlet WO2018 / 199085 Pamphlet Japanese Unexamined Patent Publication No. 2016-150944

In the present invention, gravure or flexographic ink has good printability, good lamination strength in a laminate, and less influence of elution into the contents in a packaging bag using the laminate, and a printed matter. An object of the present invention is to provide a gravure or flexographic ink using a polyurethane resin derived from biomass, which has a low odor.

As a result of diligent studies in view of the above circumstances, it has been found that the present invention can be solved by using the gravure or flexographic ink described below, and the present invention has been made.

That is, the present invention is a gravure or flexographic ink having a binder resin containing a biomass polyurethane resin.
The polyurethane resin contains the structural unit derived from a polyester polyol comprising a condensation reaction of a dibasic acid and a diol, the dibasic acid, biomass dibasic acid is a cell Bhasin acid containing more than 65 wt%, the Diols relate to gravure or flexo inks, which include branched diols and linear diols and have a mass ratio (branched diol: linear diol) of 30:70 to 70:30.
(However, this does not apply when the binder resin contains nitric acid cotton.)

The present invention also relates to the above-mentioned gravure or flexo ink in which the dibasic acid is composed only of biomass dibasic acid which is succinic acid and sebacic acid, or is composed only of biomass dibasic acid which is sebacic acid. ..

The present invention also relates to the above-mentioned gravure or flexo ink in which the mass ratio of the branched diol and the linear diol (branched diol: linear diol) is 10:90 to 90:10.

The present invention further relates to the above-mentioned gravure or flexo ink containing a vinyl chloride copolymer resin and / or a cellulosic resin.

The present invention also relates to the above-mentioned gravure or flexographic ink in which the biomass degree of the biomass polyurethane resin is 40 to 100% by mass.

The present invention also relates to a printed matter having a printed layer made of the above-mentioned gravure or flexographic ink on the base material 1.

The present invention also relates to a laminate having at least a base material 1, a printing layer made of the above-mentioned gravure or flexographic ink, and a base material 2 in this order.

The gravure or flexographic ink of the present invention has good printability, good lamination strength in a laminated body, less influence of elution into the contents in a packaging bag using the laminated laminated body, and odor of printed matter. It was possible to provide a gravure or flexographic ink using a polyurethane resin derived from biomass with a small amount of ink.

Hereinafter, the gravure or flexo ink of the present invention will be described.

The present invention is a gravure or flexographic ink having a binder resin containing a biomass polyurethane resin.
Part or all of the polyurethane resin contains a structural unit derived from a polyester polyol composed of a dibasic acid and a diol. Part or all of the dibasic acid is at least one biomass dibasic acid selected from succinic acid, sebacic acid and dimer acid. In addition, the diol includes a branched diol and a linear diol.
By containing the biomass polyurethane resin as a binder resin, it contributes to environmental conservation, and the polyurethane resin contains at least one kind of biomass dibasic acid selected from succinic acid, sebacic acid and dimer acid, and branched diols and linear diols. By containing a polyester structure made of a diol containing, the effect of imparting appropriate hardness and flexibility as a binder resin is obtained. As a result, it is considered that it contributes to the improvement of characteristics such as printability and laminate strength.

In this specification, "gravure or flexographic ink" may be simply referred to as "ink" or "printing ink", but they are synonymous with each other.
Unless otherwise specified,% and parts represent mass% and parts by mass, respectively.

(Binder resin)
The binder resin refers to a binder resin component in gravure or flexo ink. The binder resin is preferably contained in an amount of 2 to 25% by mass, preferably 4 to 20% by mass, in the total mass of the ink.

(Biomass polyurethane resin)
In the present invention, the biomass polyurethane resin refers to a resin having a biomass degree greater than 0, which will be described later. The biomass polyurethane resin is preferably contained in an amount of 30% by mass or more, more preferably 40% by mass or more, and further preferably 60% by mass or more in the total mass of the polyurethane resin.
The biomass polyurethane resin in the present invention functions as a binder resin. The mass average molecular weight of the biomass polyurethane resin is preferably 1000 to 100,000. More preferably, it is 30,000 to 80,000. When the mass average molecular weight is in the range of 1000 to 100,000, the laminate strength tends to improve.

From the concept of carbon neutral, the biomass degree of the biomass polyurethane resin in the present invention is preferably 40% by mass to 100% by mass, and more preferably 45% by mass to 100% by mass. Further, the biomass degree in the non-volatile content of the gravure or flexo ink having the binder containing the biomass polyurethane resin in the present invention, that is, the biomass degree of the printing layer is preferably 5% by mass or more, preferably 7% by mass or more. Is preferable, and 10% by mass is still more preferable.

The biomass polyurethane resin in the present invention is a polyurethane resin obtained by condensing a polyol and a polyisocyanate, a urethane prepolymer having an isocyanate group at the terminal which is a condensation reaction product of the polyol and the polyisocyanate, and a polyamine. A polyurethane resin (polyurethane urea resin) obtained by a reaction (referred to as chain extension) is preferable. It is particularly preferable that the polyol contains a high molecular weight polyol. It should be noted that any one of polyol, polyisocyanate and polyamine needs to contain a biomass-derived component.
Such a biomass polyurethane resin can be produced, for example, by the method described in WO2018 / 199085 Pamphlet and JP-A-2018-131624, and the above polyol, polyisocyanate and polyamine residues are subjected to a condensation reaction and then biomass. It is a structural unit of polyurethane resin.

The polymer polyol contains a polyester polyol obtained by reacting the biomass dibasic acid described later as a raw material component, and preferably has a mass average molecular weight of 400 to 10,000. The raw material polyol preferably contains a polyester polyol in an amount of 50% by mass or more, and more preferably 70% by mass or more.
Further, a polymer polyol other than the polyester polyol may be used in combination. Examples of such polymer polyols include polyether polyols, polycarbonate polyols and polyolefin polyols. These are preferably used in an amount of 50% by mass or less based on the total amount of the raw material polyol. As the polymer polyol used in combination with the polyester polyol, a polyether polyol is preferable from the viewpoint of plate fogability, and among the polyether polyols, polytrimethylene glycol, polytetramethylene glycol, polypropylene glycol, polyethylene glycol and copolymerization thereof. It is preferably a thing.

(Polyester polyol)
The polyester polyol contains a structural unit derived from a polyester polyol obtained by a condensation reaction of a dibasic acid and a diol, and a part or all of the dibasic acid is a biomass dibasic acid. Here, the biomass dibasic acid is a biomass-derived dibasic acid, but in the present invention, at least one kind of biomass dibasic acid selected from succinic acid, sebacic acid and dimer acid is essential. The biomass dibasic acid needs to be contained in an amount of 65% by mass or more, preferably 70% by mass or more, and preferably 85% by mass or more in the total mass of the diprotic acid as a raw material of the polyester polyol. It is more preferable, and it is more preferable that it consists of only biomass dibasic acid. Further, it is preferable that the total amount of biomass dibasic acid contains 65% by mass or more of at least one type of biomass dibasic acid selected from succinic acid, sebacic acid and dimer acid. Further, it is still preferable that the dibasic acid is composed of at least one selected from succinic acid, sebacic acid and dimer acid, and the form of the dibasic acid consisting of only one of them is also preferable. At least one type of biomass dibasic acid selected from succinic acid, sebacic acid and dimer acid can be obtained as a commercial product of Itoh Oil Chemicals, Inc., for example.

The dibasic acid may contain a dibasic acid other than biomass dibasic acid, and the dibasic acid includes adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, and oxalic acid. Examples thereof include malonic acid, glutaric acid, pimelli acid, speric acid, azelaic acid, trimellitic acid, pyromellitic acid and the like. In addition, it does not exclude succinic acid, sebacic acid and dimer acid that are not derived from biomass.

The diol contains both a branched diol and a linear diol. As a result, the lamination strength in the laminate becomes better. Here, the linear diol is a diol having 2 or more atoms, and refers to an alkylene glycol, a dialkylene glycol, a trialkylene glycol or other diol. Further, the branched diol refers to a diol in which at least one hydrogen atom of the hydrocarbon group of the alkylene glycol is substituted with a hydrogen atom other than the hydrogen atom.

Since the linear diol imparts crystallinity and the branched diol imparts flexibility, the polyurethane resin as the binder resin has a tough ink film and high lamination strength can be obtained due to the balance.

Examples of the branched diol include 2-butyl-2-ethyl-1,3-propanediol (hereinafter, also referred to as BEPG), 2-methyl-1,3-propanediol (hereinafter, also referred to as MPO), and the like. 3-Methyl 1,5-pentanediol (also referred to as MPD), neopentyl glycol (also referred to as NPG), 1,2-propylene glycol (hereinafter also referred to as PG), 2,4-diethyl-1,5-pentane Examples thereof include diol, 1,3-butanediol, and dipropylene glycol.
In the present invention, at least one branched diol selected from MPO, MPD, BEPG, NPG, PG, 2,4-diethyl-1,5-pentanediol is preferable, and NPG and / or BEPG is more preferable. It is particularly preferable to use BEPG.

The linear diol is preferably alkylene glycol, and such compounds include ethylene glycol (also referred to as EG), diethylene glycol, 1,3-propanediol (also referred to as 1,3PD), and 1,4-. Butanediol (also referred to as 1,4-BD), 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,4-butinediol, 1,4 -Butylenediol, diethylene glycol, triethylene glycol and the like can be mentioned.
Of these, linear diols having 8 or less carbon atoms, preferably 6 or less carbon atoms are preferable, and EG, 1,3PD, 1,4-BD, 1,5-pentanediol, 1,6-hexanediol, 1,8- Octanediol, etc. are preferred. Further, from the viewpoint of biomass degree and physical properties, EG, 1,3PD and 1,4-BD are particularly preferable.

In the present invention, the mass ratio of the branched diol and the linear diol (branched diol: linear diol) in the total diol of the polyester polyol is 10:90 to 90:10 from the viewpoint of the lamination strength. It is preferably 20:80 to 80:20, still more preferably. It is more preferably 30:70 to 70:30.

The branched diol unit and the linear diol unit may each be present in one polyester polyol, and a polyester polyol containing only the branched diol unit and a polyester polyol containing only the linear diol unit may be present. It may be used as a raw material for a mixture and may be used as a biomass urethane resin. Approximately the same effect can be obtained.

The polyisocyanate in the present invention is preferably diisocyanate, and as such a compound, various known diisocyanates of aromatic, aliphatic or alicyclic group can be used. For example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzylisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3- Phenylene diisocyanate, 1,4-phenylenedi isocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4- Trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexanediisocyanate, m- Typical examples include tetramethylxylylene diisocyanate and dimerized isocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group. These can be used alone or in combination of two or more. Of these, isophorone diisocyanate, tolylene diisocyanate, and 4,4'-diphenylmethane diisocyanate are preferable, and isophorone diisocyanate is more preferable from the viewpoint of solubility.

The polyamine is preferably an organic diamine, and examples of such diamines include ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, and dicyclohexylmethane-4,4'-diamine. In addition, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyro Amines having a hydroxyl group in the molecule, such as pillethylenediamine and di-2-hydroxypyropyrethylenediamine, can also be used. These organic diamines can be used alone or in combination of two or more, but isophorone diamine is preferable. In addition, diethylenetriamine, iminobispropylamine: (IBPA, 3,3'-diaminodipropylamine), N- (3-aminopropyl) butane-1,4-diamine: (spermidine), 6,6-iminodihexylamine , 3,7-Diazanonan-1,9-diamine, N, N'-bis (3-aminopropyl) ethylenediamine and other polyfunctional amines having 3 or more amino groups can be used in combination with the above organic amines.

In the present invention, the polyurethane resin preferably has an amine value. The amine value of the polyurethane urea resin is preferably 1 to 13 mgKOH / g, and when it is within this range, the lamination strength with respect to the substrate tends to be improved.

In the chain extension reaction using a polyamine, a monoamine may be used as a reaction terminator. Examples of the reaction terminator include dialkylamines such as dibutylamine, diethylamine, and dipropylamine, as well as monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane, and the like. Amines having a hydroxyl group such as the above can also be used.

In the gravure or flexo ink using the biomass polyurethane resin in the present invention, various resins can be used in combination in addition to the biomass polyurethane resin depending on the application and the base material. Examples of resins used include biomass polyurethane resins and polyurethane urea resins other than those described above, vinyl chloride copolymer resins, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, polyamide resins, and cellulose-based resins. Nitrocellulose resin, acrylic resin, polyester resin, alkyd resin, polyvinyl chloride resin, rosin resin, rosin-modified maleic acid resin, terpene resin, phenol-modified terpene resin, ketone resin, cyclized rubber, rubber chloride, polybutyral, petroleum Examples thereof include resins and modified resins thereof. These resins can be used alone or in admixture of two or more, and among them, vinyl chloride coweight resin and / or cellulosic resin are preferable. The content thereof is preferably 1 to 6% by mass in the total mass of the ink. The mass ratio of the polyurethane resin containing the biomass polyurethane resin to the vinyl chloride coweight resin and / or the cellulosic resin is preferably 95: 5 to 30:70, and is preferably 95: 5 to 50:50. Is more preferable, and it is more preferable to include it at 90: 10 to 65:35.
The total amount of the polyurethane resin containing the biomass polyurethane resin and the vinyl chloride coweight resin and / or the cellulosic resin is preferably 60% by mass or more, and more preferably 70% by mass or more in the total mass of the binder resin. , 80% by mass or more is more preferable.

<Vinyl chloride copolymer resin>
The vinyl chloride copolymer resin is not particularly limited as long as it contains a structural unit derived from vinyl chloride and a structural unit derived from other monomers. Of these, vinyl chloride-vinyl acetate copolymer resin and vinyl chloride-acrylic copolymer resin are preferable.

<Vinyl chloride-vinyl acetate copolymer resin>
The vinyl chloride-vinyl acetate copolymer resin is a copolymer of vinyl chloride and vinyl acetate, and the molecular weight is preferably 5,000 to 100,000 with a weight average molecular weight of 20,000 to 70,000. Is more preferable. The structure derived from the vinyl acetate monomer in 100% by mass of the solid content of the vinyl chloride-vinyl acetate copolymer is preferably 1 to 30% by mass, and the structure derived from the vinyl chloride monomer is preferably 70 to 95% by mass. .. In this case, the solubility in an organic solvent is improved, and the adhesion to the base material, the physical characteristics of the film, the lamination strength and the like are improved.
Further, in order to improve the solubility in an organic solvent, those containing a hydroxyl group derived from vinyl alcohol by a saponification reaction or copolymerization are more preferable, and the hydroxyl value is preferably 20 to 200 mgKOH / g. The glass transition temperature is preferably 50 ° C to 90 ° C.

<Vinyl chloride-acrylic copolymer resin>
The vinyl chloride-acrylic copolymer resin is mainly composed of a copolymer resin of a vinyl chloride monomer and an acrylic monomer, and the acrylic monomer has improved adhesiveness to a base material and solubility in an organic solvent (meth). ) It is preferable to contain an acrylic acid hydroxyalkyl ester. The acrylic monomer may be blocked or randomly incorporated into the main chain of polyvinyl chloride, or may be graft-polymerized on the side chain of polyvinyl chloride. The vinyl chloride-acrylic copolymer resin preferably has a weight average molecular weight of 10,000 to 100,000, and more preferably 30,000 to 70,000. The hydroxyl value is preferably 20 to 200 mgKOH / g, and the glass transition temperature is preferably 50 ° C to 90 ° C.

The structure derived from the vinyl chloride monomer in the vinyl chloride-acrylic copolymer resin is preferably 70 to 95% by mass based on 100% by mass of the vinyl chloride-acrylic copolymer resin solid content. In this case, the solubility in an organic solvent is improved, and the adhesion to the base material, the physical characteristics of the film, the lamination strength and the like are improved.

In the following description, (meth) acrylic or (meth) acrylate means methacrylic and acrylic, methacrylate and acrylate, respectively.

The acrylic monomer preferably contains one having a hydroxyl group, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth). (Meta) such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate. ) Acrylic acid hydroxyalkyl ester, glycol mono (meth) acrylate such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, caprolactone modified (meth) Examples thereof include acrylate and hydroxyethyl acrylamide. Among these, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl acrylate are more preferable because they improve the solubility in a solvent. These can be used alone or in combination of two or more. An acrylic monomer other than the above may be contained at any time.

<Cellulose resin>
Examples of the cellulose-based resin include nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, hydroxyalkyl cellulose, carboxyalkyl cellulose and the like, and the above alkyl groups include, for example, methyl group, ethyl group, propyl group and isopropyl group. Examples thereof include a butyl group, an isobutyl group, a pentyl group, a hexyl group and the like, and an alkyl group may further have a substituent. Among them, at least one selected from cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose is preferable. The molecular weight preferably has a weight average molecular weight of 5,000 to 200,000, and more preferably 10,000 to 80,000. Further, it is preferable that the glass transition temperature is 100 ° C. to 160 ° C. The nitrogen content of the nitrocellulose is preferably 10 to 13% by mass, and more preferably 10.5 to 12.5% by mass.

(Pigment)
The gravure or flexo ink in the present invention preferably contains a pigment as a colorant, and preferably an inorganic pigment or an organic pigment. C.I. described in the color index. I. Pigments can be used as appropriate.
Examples of the inorganic pigment include titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, aluminum hydroxide, chromium oxide, silica, carbon black, aluminum and mica (mica). Titanium oxide is preferable as the white pigment, and titanium oxide having a basic pigment surface is more preferable, from the viewpoints of coloring power, hiding power, chemical resistance, and weather resistance. Although aluminum is in the form of powder or paste, it is preferably used in the form of paste from the viewpoint of handleability and safety, and either leafing or non-leafing may be used. Barium sulfate, calcium carbonate, and aluminum hydroxide are called extender pigments and are used as bulking agents to improve fluidity, strength, and optical properties.
The organic pigments are not limited to the following examples, but are soluble azo type, insoluble azo type, azo type, phthalocyanine type, halogenated phthalocyanine type, anthraquinone type, anthraquinone type, dianthraquinone type, anthrapyrimidine type, Perylene-based, perinone-based, quinacridone-based, thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, azomethinazo-based, flavanthron-based, diketopyrrolopyrrole-based, isoindoline-based, indanslon-based, carbon black-based, etc. Pigments can be mentioned. Also, for example, Carmin 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmin FB, Chromophthal Yellow, Chromophthal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indance. Ron blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigment, etc. Can be used together at any time.

The pigment is preferably contained in an amount sufficient to secure the density and coloring power of the ink, that is, in a ratio of 1 to 50% by mass with respect to the total mass of the printing ink. It is still preferable that it is contained in an amount of 3 to 25% by mass.

(Other additives)
The ink of the present invention is a leveling agent, a defoaming agent, a wax, a silane coupling agent, a plasticizer, a light stabilizer, silica particles, an infrared absorber, an ultraviolet absorber, a fragrance, a flame retardant, and a curing agent, if necessary. Additives such as agents can also be included.

(Organic solvent)
The ink of the present invention preferably contains an organic solvent as a liquid medium. The organic solvent used is preferably used as a mixed solvent, such as aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, isopropyl acetate and isobutyl acetate. , Ester-based organic solvents, alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and other known organic solvents can be used. Of these, an organic solvent (non-toluene-based organic solvent) that does not contain an aromatic organic solvent such as toluene or xylene is more preferable. More preferably, it is an organic solvent that does not contain an aromatic organic solvent and / or a ketone-based organic solvent such as methyl ethyl ketone (hereinafter referred to as "MEK"), and the ester-based organic solvent is the main component (50% or more) in the organic solvent. ) Is preferably contained. In particular, those containing an ester-based organic solvent and an alcohol-based organic solvent are preferable.

(Ink manufacturing method)
The gravure or flexo ink in the present invention can be produced by dispersing a pigment in an organic solvent with a binder resin or the like using a disperser, and mixing the obtained pigment dispersion with a binder resin, various additives, an organic solvent or the like. .. As the disperser, generally used, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used. The particle size distribution of the pigment in the pigment dispersion is adjusted by appropriately adjusting the size of the pulverized media of the disperser, the filling rate of the pulverized media, the dispersion treatment time, the discharge rate of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to. Further, in the present invention, it can also be applied to a medium or the like containing no pigment.

The viscosity of the gravure or flexo ink is in the range of 10 mPa · s or more at 25 ° C. from the viewpoint of preventing the pigment from settling and appropriately dispersing, and 1000 mPa · s or less from the viewpoint of workability efficiency during ink production and printing. Is preferable. It is still more preferable that it is 20 to 500 mPa · s. For the above viscosity, the viscosity value measured at 25 ° C. with a B-type viscometer manufactured by Tokimec Co., Ltd. can be adopted.

(Hardener)
The gravure or flexo ink is preferably used as a two-component gravure or flexo ink by adding an isocyanate-based curing agent in order to improve the lamination strength. Examples of such isocyanate-based curing agents include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and hexamethylene diisocyanate (HDI), which are adduct-type polyisocyanate (adduct-type), biuret-type polyisocyanate (biuret-type), and isocyanate, respectively. Nurate-type polyisocyanates (isocyanurates) and the like can be preferably used, for example, an adduct form obtained from the reaction of 1 mol of trimethylolpropane and 3 mol of HDI, a biuret form obtained by the reaction of 1 mol of water and 3 mol of HDI, and the like. Examples thereof include isocyanurates obtained from the cyclic trimerization reaction of HDI. When used as a two-component type, the amount of the polyisocyanate-based curing agent added is preferably 0.5 to 10% by mass, preferably 0.5 to 5% by mass, based on the total amount of the ink of the present invention.

(Printing of gravure or flexo ink)
The ink in the present invention can also be used in a gravure printing method and a flexographic printing method. In gravure printing, it is diluted with a diluting solvent to a viscosity and concentration suitable for printing and supplied to each printing unit alone or in combination.

<Gravure printing>
(Gravure version)
When the gravure or flexo ink in the present invention is gravure-printed, it is printed using a gravure plate. In the present invention, the gravure plate is a metal cylindrical one, and recesses are created in each color by engraving, corrosion, or laser. There are no restrictions on the use of engraving and laser, and it can be set arbitrarily according to the pattern. As the number of lines, those of 100 lines to 300 lines / inch are appropriately used, and the larger the number of lines, the higher the definition of printing.
(Printer)
As the printing machine, a printing machine provided with the above gravure plate can be preferably used. Normally, a printing unit is installed for each color, and a doctor blade that scrapes ink at the same time as the gravure plate rotates is placed in each unit, and the base material passes through each printing unit and is intaglio printed before being wound into a film. It will be a gift. It is possible to use a finisher roll for the gravure version as the case may be. In addition, each unit is provided with a drying oven, and the printed base material is dried through the oven. The drying temperature is usually about 40 to 60 ° C.

<Flexographic printing>
(Flexographic version)
Examples of the plate used for flexographic printing in the present invention include a photosensitive resin plate that utilizes ultraviolet curing by a UV light source or an elastomer material plate that uses a direct laser engraving method. Regardless of the method of forming the image portion of the flexographic plate, a plate having a screening line number of 75 lpi or more is used. Any sleeve or cushion tape can be used to attach the plate.
(Printer)
Flexographic printing machines include CI type multicolor flexographic printing machines, unit type multicolor flexographic printing machines, etc., and the ink supply method can be a chamber method or a two-roll method, and an appropriate printing machine can be used. can.

<Base material 1>
The gravure or flexographic ink of the present invention is printed on the base material 1 or on the front surface or the back surface of the base material 1 of the laminate containing the base material 1 and the base material 2 to obtain a printed matter.
Examples of the base material to which the gravure or flexo ink of the present invention can be applied include polyethylene, polypropylene and other polyolefin base materials, polycarbonate base materials, polyester base materials (polyethylene terephthalate, polylactic acid, etc.), polystyrene base materials, AS resin, ABS resin and the like. Polystyrene-based base material, polyamide base material, polyvinyl chloride base material, various base materials of polyvinylidene chloride, cellophane base material, paper base material, aluminum foil base material, etc., or a film or sheet made of a composite material thereof. There is something like that. Of these, polyester base materials and polyamide base materials having a high glass transition temperature are preferably used.

The surface of the base material may be coated with a metal oxide or the like by vapor deposition coating treatment and / or a coating treatment such as polyvinyl alcohol. Examples include AE and IB-PET-PXB manufactured by Dai Nippon Printing Co., Ltd. Further, if necessary, those treated with additives such as antistatic agents and ultraviolet protective agents, and those treated with corona treatment or low temperature plasma treatment on the surface of the base material can also be used.

<Base material 2>
The base material 2 may be the same as that of the base material 1, and may be the same or different. It is preferably a thermoplastic base material (sometimes referred to as a sealant), and a non-stretched polyethylene base material, a non-stretched polypropylene base material, a non-stretched polyester base material, or the like is preferable.

<Laminated body>
It is also possible to manufacture a laminate using the printed matter. Such a laminate is a laminate having at least a base material 1, a printing layer, and a base material 2 in this order. It is preferable to use a laminate having at least a base material 1, a printing layer, an adhesive layer, and a base material 2 in this order.
The laminate of the present invention can be obtained by providing an adhesive layer on a printed matter printed with gravure or flexographic ink and laminating (laminating) it with the base material 2. A dry laminating method or the like can be mentioned as a typical example of laminating processing. The dry laminating method is a method in which an adhesive is applied onto a printed layer of a printed matter, dried, and thermocompression bonded to a sealant for laminating.

<Adhesive layer>
The adhesive layer is obtained by applying an adhesive and drying it. The adhesive is preferably a two-component adhesive composed of a mixture of a polyol and an isocyanate curing agent, and examples of the polyol include polyester-based adhesives and polyether-based adhesives. Specific examples thereof include TM-250HV / CAT-RT86L-60, TM-550 / CAT-RT37, TM-314 / CAT-14B manufactured by Toyo Morton Co., Ltd.

Hereinafter, the present invention will be described in detail with reference to examples, but the following embodiments are only examples of the present invention, and the present invention is not limited to these examples. Unless otherwise specified, parts and% in the present invention represent parts by mass and% by mass. However, Examples 1, 2, 3, 5, 11 and 12 are reference examples.

<Measuring method of amine value>
The amine value was determined according to the following method according to JIS K0070 with the same amount of potassium hydroxide mg as the equivalent of hydrochloric acid required to neutralize the amino group contained in 1 g of the resin.
The sample was precisely weighed in an amount of 0.5 to 2 g (sample solid content: Sg). To the precisely weighed sample, 50 mL of a mixed solution of methanol / methyl ethyl ketone = 60/40 (mass ratio) was added and dissolved. Bromophenol blue was added to the obtained solution as an indicator, and the obtained solution was titrated with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). With the point where the color of the solution changed from green to yellow as the end point, the amine titer was determined by the following (Equation 1) using the titration amount (AmL) at this time.
(Formula 1) Amine value = (A × f × 0.2 × 56.108) / S [mgKOH / g]

<Measurement method of number average molecular weight (Mn) and mass average molecular weight (Mw)>
The number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured by using GPC (gel permeation chromatography) "Shodex GPC System-21" manufactured by Showa Denko KK. GPC is a liquid chromatography in which a substance dissolved in a solvent is separated and quantified by the difference in its molecular size. The solvent is tetrohydrofuran, and the molecular weight is determined in terms of polystyrene.

<Measurement method of hydroxyl value>
It was obtained according to the method described in JIS K0070.

<Measurement method of acid value>
It was obtained according to the method described in JIS K0070.

[Synthesis Example 1-1] (Synthesis of Polyester Polyol A1)
2.6 parts of 1,3-propanediol (hereinafter abbreviated as 1,3-PD), 2-butyl2-ethyl1, in a round-bottom flask equipped with a stirrer, thermometer, water divider and nitrogen gas introduction tube. 49.4 parts of 3-propanediol (hereinafter abbreviated as BEPG), 48 parts of succinic acid, and 0.002 part of tetrabutyl titanate were charged, and esterification was carried out for 8 hours while removing water generated by condensation at 230 ° C. under a nitrogen stream. went. After confirming that the acid value of the polyester was 15 or less, the degree of vacuum was gradually increased by a vacuum pump to complete the reaction. As a result, polyester polio (A1) having a number average molecular weight of 2000, a hydroxyl value of 56.1 mgKOH / g, an acid value of 0.3 mgKOH / g, and a biomass degree of 50.6% was obtained.

[Synthesis Example 1-2-1-16] (Synthesis of Polyester Polyols A2 to A16)
Polyester polyols A2 to A16 were obtained in the same manner as in Synthesis Example 1-1 except that the raw materials and the charging ratios shown in Table 1 were used. The abbreviations described in the table represent the following.
BEPG: 2-butyl-2-ethyl-1,3-propanediol (derived from petroleum)
MPO: 2-Methyl-1,3-propanediol (derived from petroleum)
MPD: 3-Methyl-1,5-pentanediol (derived from petroleum)
NPG: Neopentyl glycol (plant-derived biomass 40%)
PG: 1,2-Propylene glycol (100% plant-derived biomass)
EG: Ethylene glycol (100% plant-derived biomass)
1,3-PD: 1,3-Propanediol (100% plant-derived biomass)
In the above, the biomass degree of NPG is derived from the catalog value of Perstoop.
-The dibasic acids in the table have the following biomass degrees.
Succinic acid: (100% biomass-derived biomass)
Adipic acid: (derived from petroleum)
Sebacic acid: (100% biomass-derived biomass)
Dimer acid: (100% biomass-derived biomass)

The degree of biomass refers to the ratio of plant-derived or other biomass-derived compounds contained in the compound.
Biomass degree = 100 × mass of biomass-derived component of the relevant compound / total mass of the relevant compound.
However, if the compound is a reaction product of a biomass-derived raw material and a non-biomass-derived raw material, it is calculated by converting it into a raw material before the reaction. For example, in the case of a polyester resin (polyester polyol) which is a reaction product of dibasic acid and diol.
Biomass degree = 100 x (biomass dibasic acid + biomass-derived diol) / (all dibasic acids + all diols)
"All dibasic acids + all diols" refers to the sum of biomass-derived and non-biomass-derived dibasic acids, and biomass-derived and non-biomass-derived diols.

[Comparative Synthesis Examples 1-1 to 1-3] (Synthesis of Polyester Polyols B1 to B3)
Polyester polyols B1 to B3 were obtained in the same manner as in Synthesis Example 1-1 except that the raw materials and the charging ratios shown in Table 1 were used.

[Synthesis Example 2-1] (Synthesis of Polyurethane Resin P1)
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, 23.6 parts of polyester polyol A1, 4.68 parts of isophorone diisocyanate (hereinafter abbreviated as IPDI), ethyl acetate 7. 5 parts and 0.003 parts of tin 2-ethylhexanoate were charged and reacted at 120 ° C. for 6 hours under a nitrogen stream, and 7.5 parts of propyl acetate was added and cooled to obtain a solution of the terminal isocyanate prepolymer. Next, a solution of the obtained terminal isocyanate prepolymer was gradually added to a mixture of 1.72 parts of isophorone diamine (hereinafter also abbreviated as IPDA), 34 parts of ethyl acetate and 21 parts of isopropyl alcohol (hereinafter also abbreviated as IPA) at room temperature. Then, the reaction was carried out at 50 ° C. for 1 hour to obtain a polyurethane resin P1 solution having a solid content of 30%, a mass average molecular weight of 70,000 and an amine value of 4 mgKOH / g and a biomass degree of 40% by mass.

[Synthesis Example 2-2-2-24] (Synthesis of Polyurethane Resins P2-P24)
Polyurethane resins P2 to P24 were obtained in the same manner as in Synthesis Example 2-1 except that the raw materials and the charging ratios shown in Tables 2-1 and 2-2 were used. In Synthesis Example 2-17 and Synthesis Example 2-18, 11.8 parts of polyester polyol B1 was used in combination. The degree of biomass etc. is shown in the same table.

[Comparative Synthesis Example 2-1 to 2-3]
Polyurethane resins PP1 to PP3 were obtained in the same manner as in Synthesis Example 2-1 except that the raw materials and the charging ratios shown in Table 2-3 were used. The degree of biomass etc. is shown in the same table.

[Example 1] (Manufacturing of ink S1)
10 parts of copper phthalocyanine indigo (LIONOL BLUE FG-7330 manufactured by Toyo Color Co., Ltd.), 10 parts of polyurethane resin P1 solution, vinyl chloride-vinyl acetate resin solution (hydroxyl value is 140 mgKOH / g, mass average molecular weight is 50,000 vinyl chloride-acetic acid) After mixing 5.0 parts of vinyl copolymer resin solid content 30% solution and 10 parts of mixed solvent (propyl acetate / IPA = 75/25 (mass ratio)) with stirring and kneading with a sand mill, polyurethane resin (B1) 30 35 parts of the mixed solvent (normal propyl acetate / isopropyl alcohol = 75/25 (mass ratio)) were stirred and mixed to obtain indigo printing ink S1.

[Examples 2-34] (Manufacturing of inks S2-S34)
Inks S2 to S34 were obtained in the same manner as in Example 1 except that the raw materials and the charging ratios shown in Tables 3-1 and 3-2 were used. The description in the table shows the following.
Titanium Oxide: Titanium Oxide Titanium JR-805 manufactured by TAYCA Corporation
Nitrocellulose: Nitrocellulose solid content 30% solution with mass average molecular weight of 40,000 and nitrogen content of 12% by mass

[Comparative Examples 1 to 3] (Manufacturing of inks SS1 to SS3)
Inks SS1 to SS3 were obtained in the same manner as in Example 1 except that the raw materials and the charging ratios shown in Table 3-3 were used.

[Creation of printed matter using ink S1]
The viscosity of the ink S1 was diluted with a propyl acetate / IPA mixed solvent (mass ratio 70/30) to a viscosity of 15 seconds (at 25 ° C.) in Zahn Cup # 3 (manufactured by Rigo Co., Ltd.), and a plate depth of 30 μm gravure plate was prepared. Printing on the corona-treated surface of single-sided corona-treated polypropylene (OPP) film (Pyrene P2161 manufactured by Toyo Spinning Co., Ltd.) and single-sided corona-treated polyethylene terephthalate (PET) film (E5100 # 12 manufactured by Toyo Spinning Co., Ltd.) It was dried at 40 to 50 ° C. to obtain a printed matter (OPP, PET) using the ink S1.

[Creation of printed matter using inks S2 to S34 and inks SS1 to SS3]
Printed matter (OPP, PET) using inks S2 to S34 and inks SS1 to SS3 were obtained in the same manner as in the example of printed matter using ink S1 except that inks S2 to S34 and inks SS1 to SS3 were used. ..

[evaluation]
Using the inks S1 to S34 (Example), SS1 to SS3 (Comparative Example) and their printed matter (OPP, PET) obtained in the above Examples and Comparative Examples, the taste of the contents is obtained by the method described below. The test and the evaluation of the laminate strength were performed.

[Elution component test (PET / CPP composition)]
On the printed matter of the PET film of the inks S1 to S34 (Example) and SS1 to SS3 (Comparative Example) obtained in the above Examples and Comparative Examples, a dry laminating machine was used at a line speed of 40 m / min. An adhesive was applied, and at the same time, it was laminated with a non-stretched polypropylene (CPP) film (ZK93KM, manufactured by Toray Co., Ltd., having a thickness of 60 μm) to obtain a laminated laminate having a printed layer.
As the adhesive used for the dry laminate, TM-550 / CAT-RT37 manufactured by Toyo Morton Co., Ltd. was used. After that, the laminate was cut into a size of 12 cm in width and 22 cm in length, and the edges were heat-sealed (temperature: 190 ° C., pressure: 2 kgf, time: 1 second) with the CPP surfaces inside to make a packaging bag, and water was used as the content. Was filled and boiled at 85 ° C. for 20 minutes.
Boiled water was analyzed by gas chromatography-mass spectrometry (GC / MS) to confirm the presence or absence of peaks of organic components. The GC / MS apparatus and columns are as follows.
Equipment: HP-GC6890N / MSD5793 (manufactured by Agilent Technologies) / TDS (manufactured by Agilent Technologies) Column: HP-5 (inner diameter 0.32 mm / length 60 m / thickness 1.00 μm) (Agilent Technologies, Inc.) Made)
(Evaluation criteria)
5: No organic matter other than the cyclic diester was detected, and the boiled water was odorless. (Yu)
4: Organic substances other than cyclic diester were detected, and the boiled water was odorless. (good)
3: Organic substances other than cyclic diesters were detected, and the boiled water had a slight odor. (Yes)
2: Organic substances other than cyclic diester were detected, and the boiled water had an odor. (No)
1: A peak due to the cyclic diester was confirmed, and the boiled water had an odor. (Inferior)
The practical level is 3 to 5.

[Elution component test (PET / LLDPE composition)]
In the above dissolution test, except that linear low density polyethylene (LLDPE) (L4104 film thickness 50 μm manufactured by Toyobo Co., Ltd.) was used instead of unstretched polypropylene (CPP) film (ZK93KM film thickness 60 μm manufactured by Toray Industries, Inc.). Evaluation was performed in the same manner as above.

[Volatile / odor test]
Immediately after printing, the printed matter of the PET films of the inks S1 to S34 (Example) and SS1 to SS3 (Comparative Example) obtained in the above Examples and Comparative Examples was cut into a size of 12 cm in width and 22 cm in length and sealed in a bottle. It was placed in an oven and kept at 60 ° C. for 12 hours.
The components in the bottle were analyzed by gas chromatography-mass spectrometry (GC / MS) in the same manner as above.
(Evaluation criteria)
5: No peak due to organic matter was confirmed, and the printed matter was odorless. (Yu)
4: A peak due to organic matter was confirmed, and the printed matter was odorless. (good)
3: A peak due to organic matter was confirmed, and the printed matter had a slight odor. (Yes)
2: A peak caused by organic matter was confirmed, and the printed matter had a slightly strong odor. (No)
1: A peak caused by organic matter was confirmed, and the printed matter had a strong odor. (Inferior)
The practical level is 3 to 5.

[Laminate strength]
Immin-based anchor coating agent (EL420 manufactured by Toyo Morton Co., Ltd.) on the printed matter of the OPP film printed matter of the inks S1 to S34 (Example) and SS1 to SS3 (Comparative Example) obtained in the above Examples and Comparative Examples. A methanol solution having a solid content of 1% by mass was applied, and molten polyethylene (LC600A manufactured by Japan Polyethylene Corporation) was extruded at 320 ° C. and laminated at 18 μm using an extrusion laminating machine (manufactured by Musashinokikai) at a line speed of 100 m / min. At the same time, CPP (FCMN film thickness 20 μm manufactured by Futamura Chemical Co., Ltd.) was laminated in the same manner to obtain a laminated laminate. After the laminating process, the laminated laminate was cut into a length of 150 mm and a width of 15 mm, opened at the ink / OPP film interface, and the lamination strength in the 90 ° direction was measured using a tensile tester.
(Evaluation criteria)
5: 1.5N / 15mm or more (excellent)
4: 1.0N / 15mm or more and less than 1.5N / 15mm (good)
3: 0.8N / 15mm or more and less than 1.0N / 15mm (possible)
2: 0.5N / 15mm or more and less than 0.8N / 15mm (impossible)
1: 0.5N / less than 15mm (inferior)
The practical level is 3 to 5.

From the above results, the subject of the present application could be achieved by using the gravure or flexo ink of the present invention. Further, when a biomass polyurethane resin using a polyester polyol having a biomass-derived dibasic acid was used, the lamination strength was improved. In addition, the polyurethane resin contains a polyester structure composed of at least one biomass dibasic acid selected from succinic acid, sebacic acid and dimer acid, and a diol containing a branched diol and a linear diol to provide the content after retorting. Superior results were obtained for the odor of objects and the odor of printed matter of the present invention.

Claims (7)

A gravure or flexographic ink having a binder resin containing a biomass polyurethane resin.
The polyurethane resin contains the structural unit derived from a polyester polyol comprising a condensation reaction of a dibasic acid and a diol, the dibasic acid, biomass dibasic acid is a cell Bhasin acid containing more than 65 wt%, the The diol is a gravure or flexo ink containing a branched diol and a linear diol and having a mass ratio (branched diol: linear diol) of 30:70 to 70:30.
(However, this does not apply when the binder resin contains nitric acid cotton.) The gravure or flexo ink according to claim 1, which contains 70% by mass or more of biomass dibasic acid in 100% by mass of dibasic acid. The gravure or flexo ink according to claim 1 or 2, wherein the dibasic acid is composed only of biomass dibasic acid which is succinic acid and sebacic acid, or is composed only of biomass dibasic acid which is sebacic acid. .. The gravure or flexo ink according to any one of claims 1 to 3, further comprising a vinyl chloride copolymer resin. The gravure or flexo ink according to any one of claims 1 to 4, wherein the biomass of the polyurethane polyurethane resin has a biomass content of 40 to 100% by mass. A printed matter having a printed layer made of the gravure or flexographic ink according to any one of claims 1 to 5 on the base material 1. A laminate having at least a base material 1, a printing layer made of the gravure or flexographic ink according to any one of claims 1 to 6, and a base material 2 in this order.